Metal–metal cooperative bond activation by heterobimetallic alkyl, aryl, and acetylide PtII/CuI complexes

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

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Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

10.26434/chemrxiv.11742687.v1 ◽

2020 ◽

Author(s):

Shubham Deolka ◽

Orestes Rivada Wheelaghan ◽

Sandra Aristizábal ◽

Robert Fayzullin ◽

Shrinwantu Pal ◽

...

Keyword(s):

Alkyl Group ◽

Bond Activation ◽

Bond Cleavage ◽

Terminal Alkyne ◽

Alkyl Aryl ◽

Metal Metal ◽

The Stability ◽

Selective Formation ◽

Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

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Unsaturated, PCy2-bridged Re-M heterobimetallics (M = rhodium, iridium, palladium; Cy = cyclohexyl): metal-metal bond isomerism, reversible phosphorus-hydrogen bond activation and cooperative reactivity

Organometallics ◽

10.1021/om00098a040 ◽

1988 ◽

Vol 7 (8) ◽

pp. 1889-1891 ◽

Cited By ~ 20

Author(s):

R. Thomas. Baker ◽

Joseph c. Calabrese ◽

Timothy E. Glassman

Keyword(s):

Hydrogen Bond ◽

Bond Activation ◽

Metal Bond ◽

Metal Metal

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Organorheniumhalogenide: Synthesen, Strukturen und Reaktivität gegenüber Alkinen / Organorhenium Halogenides: Synthesis, Structure and Reactivity upon Treatment with Alkynes

Zeitschrift für Naturforschung B ◽

10.1515/znb-1988-1104 ◽

1988 ◽

Vol 43 (11) ◽

pp. 1391-1404 ◽

Cited By ~ 12

Author(s):

Wolfgang A. Herrmann ◽

Roland A. Fischer ◽

Josef K. Felixberger ◽

Rocco A. Paciello ◽

Pavlo Kiprof ◽

...

Keyword(s):

Diffraction Study ◽

Single Bond ◽

X Ray Diffraction ◽

Alkyl Aryl ◽

X Ray ◽

Aluminium Powder ◽

Metal Metal ◽

Related Derivative ◽

Alkyne Complexes ◽

Powder Forming

The organorhenium(V) complexes (η5-C5Me5)ReX4 (2a, X = Cl; 2b, X = Br; Me = CH3) undergo stepwise dehalogenation upon treatment with various reducing agents, e.g. with HgCl2-activated aluminium powder, forming the isolable ReIV and ReIII dimers [η5-C5Me5)ReCl3]2 (3a) and [η5-C5Me5)ReX2]2 (4a, X = Cl;4b, X = Br), respectively. The weak metal-metal single bond of 3a (307.4(0) pm; X-ray diffraction study) is disrupted upon reaction with alkynes yielding the ReIII derivatives (η5-C5Me5)ReCl2(η2-R1CCR2) (9a-e; R1, R2: alkyl, aryl) and novel rhenium(V)- allylidenyl complexes of type (η5-C5Me5)ReCl2[η1:η3-R1CC(Cl)CHR3] (10a-d; R1: alkyl. aryl; R3: H, alkyl). Reduction of 2a (Al/HgCl2) in the presence of alkynes gives a complex reaction mixture of 9a-c, 10a - c and bis(π-alkyne) complexes [(η5-C5Me5)ReCl(η2-R1CCR2)2] + [AlCl4]-(11a-c) (X-ray diffraction study of the related derivative [(η5-C5Me5)ReBr(η2-MeCCMe)2] + [SbF6]-).

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